CA1178292A - Self-granulating reaction product of 4,4'- diphenylmethane diisocyanate and resorcinol - Google Patents
Self-granulating reaction product of 4,4'- diphenylmethane diisocyanate and resorcinolInfo
- Publication number
- CA1178292A CA1178292A CA000399042A CA399042A CA1178292A CA 1178292 A CA1178292 A CA 1178292A CA 000399042 A CA000399042 A CA 000399042A CA 399042 A CA399042 A CA 399042A CA 1178292 A CA1178292 A CA 1178292A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- resorcinol
- product
- powder
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
Abstract
Mo-2280 SELF-GRANULATING REACTION PRODUCT OF 4,4'-DIPHENYLMETHANE DIISOCYANATE AND RESORCINOL
ABSTRACT OF THE DISCLOSURE
The present invention relates to a free-flowing, dry, granular powder comprising the reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol, the product having an isocyanate group content of from 27 to 31% by weight, and to the process for manu-facture thereof.
Mo-2280
ABSTRACT OF THE DISCLOSURE
The present invention relates to a free-flowing, dry, granular powder comprising the reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol, the product having an isocyanate group content of from 27 to 31% by weight, and to the process for manu-facture thereof.
Mo-2280
Description
~8~g~, Mo- 2 2 8 0 PU-l 31 SELF-GRANULATING REACTION PRODUCT OF 4, 4 ' -DIPHENYLMETHANE DIISOCYANATE AND RESORCINOL
-BACKGROUND OF THE INVENTION
The present invention relates to a self-granulating reaction product of 4, 4 '-diphenylmethane diisocyanate and resorcinol, and to the method of prep-aration thereof.
It is known that 4, 4 ' -diphenylmethane diiso-cyanate is solid at room temperature. When such diisocyanate is stored in drums, a solid product is formed which requires heating prior to removal from the drums.
Since 4,4'-diphenylmethane diisocyanate is highly useful in the production of thermoplastic polyurethanes, cast polyurethane elastomers, and many other urethane applications, it would be highly de-sirable to be able to use 4,4'-diphenylmethane diiso-cyanate directly from the storage drums without a need to heat such drums. The present invention substantial-ly solves the problem noted above.
DESCRIPTION OF THE INVENTION
The present invention is directed to a reactionproduct of 4,4'-diphenylmethane diisocyanate and resorcinol and to the method of its manufacture. The resultant product, which generally contains from 27 to 31% by weight of isocyanate groups, is a dry, gran-ular powder which flows freely without any need for heating.
The present process broadly comprises ~i) reacting 4,4'-diphenylmethane diisocya-nate with resorcinol at a temperature of from 40 to 80C in the presence of a catalytic amount of a mate-rial which catalyzes the reaction between isocyanate groups and hydroxyl groups, Mo-2280 ~ ~'7~
(ii) allowing -the reaction mixture to exo-therm to a temperature no higher than 90C, and (iii) allowing the resultan-t product to cool to room temperature, thereby forming a free-flowing, dry, granular powder.
The product of the present invention is generally produced by mixing the two components and heating them to a temperatuxe of from 40 to 80C. The catalyst can either be added to the reaction mixture or vice versa. Similarly, the catalyst can be added before or after the heating step. A slight exotherm is generally observed. It is critical to the present invention that the heating temperature be kept at or below 80C in order to allow Eor production of the free-flowing, dry, granular powder. During the exo-therm the reaction mixture is maintained at a tempera-ture not exceeding 90C. As the exotherm s~bsides, the material upon cooling generalLy becomes a fluid slush which, if desired, can then be poured on a suitable surface, e.g., an open pan or a slowly moving conveyor ~elt. Upon standing for from 15 minutes to
-BACKGROUND OF THE INVENTION
The present invention relates to a self-granulating reaction product of 4, 4 '-diphenylmethane diisocyanate and resorcinol, and to the method of prep-aration thereof.
It is known that 4, 4 ' -diphenylmethane diiso-cyanate is solid at room temperature. When such diisocyanate is stored in drums, a solid product is formed which requires heating prior to removal from the drums.
Since 4,4'-diphenylmethane diisocyanate is highly useful in the production of thermoplastic polyurethanes, cast polyurethane elastomers, and many other urethane applications, it would be highly de-sirable to be able to use 4,4'-diphenylmethane diiso-cyanate directly from the storage drums without a need to heat such drums. The present invention substantial-ly solves the problem noted above.
DESCRIPTION OF THE INVENTION
The present invention is directed to a reactionproduct of 4,4'-diphenylmethane diisocyanate and resorcinol and to the method of its manufacture. The resultant product, which generally contains from 27 to 31% by weight of isocyanate groups, is a dry, gran-ular powder which flows freely without any need for heating.
The present process broadly comprises ~i) reacting 4,4'-diphenylmethane diisocya-nate with resorcinol at a temperature of from 40 to 80C in the presence of a catalytic amount of a mate-rial which catalyzes the reaction between isocyanate groups and hydroxyl groups, Mo-2280 ~ ~'7~
(ii) allowing -the reaction mixture to exo-therm to a temperature no higher than 90C, and (iii) allowing the resultan-t product to cool to room temperature, thereby forming a free-flowing, dry, granular powder.
The product of the present invention is generally produced by mixing the two components and heating them to a temperatuxe of from 40 to 80C. The catalyst can either be added to the reaction mixture or vice versa. Similarly, the catalyst can be added before or after the heating step. A slight exotherm is generally observed. It is critical to the present invention that the heating temperature be kept at or below 80C in order to allow Eor production of the free-flowing, dry, granular powder. During the exo-therm the reaction mixture is maintained at a tempera-ture not exceeding 90C. As the exotherm s~bsides, the material upon cooling generalLy becomes a fluid slush which, if desired, can then be poured on a suitable surface, e.g., an open pan or a slowly moving conveyor ~elt. Upon standing for from 15 minutes to
2 hours at room temperature, the product becomes a free-flowing dry, granular powder.
In addition to the critical tempera~ure noted 25 abo~e, the amount of resorcinol used also appears to be critical. In general, the amount used should be such that the isocyanate group content of the resul-tant product is from 27% to 31% by weight. The isocyanate group content of the product is preferably from 28% to 30% by weight. In general, the isocya-nate group content noted will be achieved by using from 2 to 7 and preferably from about 2.~ to 5 parts by weight of resorcinol per 100 parts by weight of Mo-2280 ~17~Z~Z
isocyanate. The melting point of the product is dependent upon the amount of resorcinol used. For e~ample, when using 2.4 parts of resorcinol, the melting point of the product is about 60C, while use of 5 parts produces a product havin~ a melting point of 90C.
Suitable catalysts must also be used, which catalysts are generally known in the art for the catal-ysis of the reaction of isocyanate groups with hydroxyl groups. It is presently preferred to utilize dibutyl-tin dilaurate and/or triethylene diamine. The catalysts should be used in catalytic amounts and are generally used in amounts of from 0.001 to 5% by weight basea on the amount of isocyanate used.
The invention is further illustrated, but is not intended to be limited by the following Examples in which all parts and percentages are by weight unless otherwise specified.
Mo-2280 . .
7~32~
EXP~IPLES
E.YAMPLE 1 _ 100 parts of 4,4'-diphenylmethane diisocyanate and 2.4 parts of resorcinol were added to a rPaction vessel and heated to about 80C with ~low stirring.
One drop of triethylene diamine and one drop of di-butyltin dilaurate were added. The solution exo-thermed slightly and turned hazy. The solution was held at about 90C for five minutes and poured into a 6" x 7" aluminum pan. After about 90 minutes, the product had slowly formed a free-flowing, ligh-t powder having an isocyanate group content of about 31% by weight.
EXP~IPLE 2 100 parts o 4,4'-diphenylmethane diisocyanate and 3 parts of resorcinol were added -to a reaction vessel and heated to 55 to 60C. One drop of dibutyl-tin dilaurate was added and a slight exotherm was observed. The mixture was cooled to abou-t 55C and poured into a 6" x 8" aluminum pan. A free-flowiIlcJ, dry powder resulted.
When the experiment was repeated using catecol, hydroquinone, 4,4'-sulphonyl diphenol, 4,4'-dihydroxy-diphenylsulfide, bisphenol A, phenol and 1,6-hexane-diol, instead of resorcinol, a powder did no-t result.
Mo-2280 P~-131
In addition to the critical tempera~ure noted 25 abo~e, the amount of resorcinol used also appears to be critical. In general, the amount used should be such that the isocyanate group content of the resul-tant product is from 27% to 31% by weight. The isocyanate group content of the product is preferably from 28% to 30% by weight. In general, the isocya-nate group content noted will be achieved by using from 2 to 7 and preferably from about 2.~ to 5 parts by weight of resorcinol per 100 parts by weight of Mo-2280 ~17~Z~Z
isocyanate. The melting point of the product is dependent upon the amount of resorcinol used. For e~ample, when using 2.4 parts of resorcinol, the melting point of the product is about 60C, while use of 5 parts produces a product havin~ a melting point of 90C.
Suitable catalysts must also be used, which catalysts are generally known in the art for the catal-ysis of the reaction of isocyanate groups with hydroxyl groups. It is presently preferred to utilize dibutyl-tin dilaurate and/or triethylene diamine. The catalysts should be used in catalytic amounts and are generally used in amounts of from 0.001 to 5% by weight basea on the amount of isocyanate used.
The invention is further illustrated, but is not intended to be limited by the following Examples in which all parts and percentages are by weight unless otherwise specified.
Mo-2280 . .
7~32~
EXP~IPLES
E.YAMPLE 1 _ 100 parts of 4,4'-diphenylmethane diisocyanate and 2.4 parts of resorcinol were added to a rPaction vessel and heated to about 80C with ~low stirring.
One drop of triethylene diamine and one drop of di-butyltin dilaurate were added. The solution exo-thermed slightly and turned hazy. The solution was held at about 90C for five minutes and poured into a 6" x 7" aluminum pan. After about 90 minutes, the product had slowly formed a free-flowing, ligh-t powder having an isocyanate group content of about 31% by weight.
EXP~IPLE 2 100 parts o 4,4'-diphenylmethane diisocyanate and 3 parts of resorcinol were added -to a reaction vessel and heated to 55 to 60C. One drop of dibutyl-tin dilaurate was added and a slight exotherm was observed. The mixture was cooled to abou-t 55C and poured into a 6" x 8" aluminum pan. A free-flowiIlcJ, dry powder resulted.
When the experiment was repeated using catecol, hydroquinone, 4,4'-sulphonyl diphenol, 4,4'-dihydroxy-diphenylsulfide, bisphenol A, phenol and 1,6-hexane-diol, instead of resorcinol, a powder did no-t result.
Mo-2280 P~-131
Claims (8)
1. A free-flowing, dry, granular powder comprising the reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol, the product having an isocyanate group content of from 27 to 31% by weight.
2. The powder of Claim 1 having an isocyanate group content of from 28 to 30% by weight.
3. The powder of Claim 1, wherein from 2 to 7 parts by weight of resorcinol are reacted per 100 parts by weight of said diisocyanate.
4. The powder of Claim 3, wherein from 2.4 to 5 parts by weight of resorcinol are reacted per 100 parts by weight of said diisocyanate.
5. The powder of Claim 1, wherein from 0.001 to 5% by weight of a catalyst for the reaction of isocyanate groups and hydroxyl groups is used during formation of the reaction product.
6. A process for the preparation of a free-flowing, dry, granular powder comprising:
(i) reacting 4,4'-diphenylmethane diiso-cyanate with resorcinol at a temperature of from 40 to 80°C in the presence of a catalytic amount of a material which catalyzes the reaction between isocyanate groups and hydroxyl groups, (ii) allowing the reaction mixture to exotherm to a temperature no higher than 90°C, and (iii) allowing the resultant product to cool to room temperature.
(i) reacting 4,4'-diphenylmethane diiso-cyanate with resorcinol at a temperature of from 40 to 80°C in the presence of a catalytic amount of a material which catalyzes the reaction between isocyanate groups and hydroxyl groups, (ii) allowing the reaction mixture to exotherm to a temperature no higher than 90°C, and (iii) allowing the resultant product to cool to room temperature.
7. The process of Claim 6, wherein the resul-tant product has an isocyanate group content of from 27 to 31% by weight.
Mo-2280
Mo-2280
8. The process of Claim 7, wherein said material is used in an amount of from 0.001 to 5% by weight based on the amount of isocyanate.
Mo-2280
Mo-2280
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US292,967 | 1981-08-14 | ||
| US06/292,967 US4344892A (en) | 1981-08-14 | 1981-08-14 | Self-granulating reaction product of 4,4'-diphenylmethane diisocyanate and resorcinol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1178292A true CA1178292A (en) | 1984-11-20 |
Family
ID=23127023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399042A Expired CA1178292A (en) | 1981-08-14 | 1982-03-22 | Self-granulating reaction product of 4,4'- diphenylmethane diisocyanate and resorcinol |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4344892A (en) |
| EP (1) | EP0072483B1 (en) |
| JP (1) | JPS5838716A (en) |
| BR (1) | BR8204767A (en) |
| CA (1) | CA1178292A (en) |
| DE (1) | DE3266837D1 (en) |
| ES (1) | ES514978A0 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043472A (en) * | 1989-12-21 | 1991-08-27 | Mobay Corporation | Storage stable solid isocyanate compositions, preparation, and method of use thereof |
| US6284846B1 (en) * | 1999-11-02 | 2001-09-04 | Ppg Industries Ohio, Inc. | Stable powder coating compositions |
| US6294619B1 (en) | 1999-11-02 | 2001-09-25 | Ppg Industries Ohio, Inc. | Stable powder coating compositions which produce consistent finishes |
| MY148143A (en) | 2006-03-03 | 2013-03-15 | Indspec Chemical Corp | Resorcinol-blocked isocyanate compositions and their applications |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3035078A (en) * | 1959-02-04 | 1962-05-15 | Allied Chem | Stabilized polyisocyanate compositions |
| DE1618380C3 (en) * | 1967-03-08 | 1975-09-11 | Bayer Ag, 5090 Leverkusen | Process for the production of a diphenylmethane diisocyanate preparation which is liquid at room temperature |
| US3997592A (en) * | 1975-11-24 | 1976-12-14 | E. I. Du Pont De Nemours And Company | Preparation of aqueous dispersions of blocked aromatic polyisocyanates |
-
1981
- 1981-08-14 US US06/292,967 patent/US4344892A/en not_active Expired - Lifetime
-
1982
- 1982-03-22 CA CA000399042A patent/CA1178292A/en not_active Expired
- 1982-08-02 DE DE8282106956T patent/DE3266837D1/en not_active Expired
- 1982-08-02 EP EP82106956A patent/EP0072483B1/en not_active Expired
- 1982-08-10 JP JP57138061A patent/JPS5838716A/en active Granted
- 1982-08-13 ES ES514978A patent/ES514978A0/en active Granted
- 1982-08-13 BR BR8204767A patent/BR8204767A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8306475A1 (en) | 1983-06-01 |
| JPS5838716A (en) | 1983-03-07 |
| BR8204767A (en) | 1983-08-02 |
| EP0072483B1 (en) | 1985-10-09 |
| US4344892A (en) | 1982-08-17 |
| DE3266837D1 (en) | 1985-11-14 |
| ES514978A0 (en) | 1983-06-01 |
| EP0072483A1 (en) | 1983-02-23 |
| JPH033686B2 (en) | 1991-01-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |